Reactivation of solid phosphoric acid catalyst



invention relates to, the reactivation of solid phosphoric acid catalyst which. has become deactivated by Un ed State P m nitrogen compounds during the polymerization of nor--,

, It is known in the art to employ. solid phosphoric acid catalyst in the polymerization of normally gaseous olefins, e.g., propylenepin order to'obtain polymers generally ranging, from the dimer to the pentamer. Solid phosphoric acid catalyst, as the term is used in this art, refers to a solid porous granular material, e.g. kieselguhr, silica gel, etc., which has been impregnated with an acid or. phosphorus,e.g.phosphorib acid, andcalcined to produce a;desired lower state of hydration of the, catalyst. The nature and preparation of the solid phosphoric acid catalyst are well'k'nownsin the polymerization art, and numerous prior disclosures set forth these features of such catalyst, .33 n V .'-.The usual practice in polymerization of olefins by means; of solid-phosphoric acid catalyst involves passing the olefin charge material througha, bed ofthe catalyst at atemperature usually within the approximaterange from 300 F. to 500 F. and 'pressure ,within the approximate range from 500 p.s :i.g.-'to 2000 psig During thepolymerization process, the catalyst graduallybecomes deactivatedas a result of contamination of the catalystbyjnitrogen compounds contained in the charge stock. The manner in which the nitrogen compounds become associatedwith the phosphoric acid catalyst is not definitely known.. The association may involve reaction ofthe nitrogencompounds with phosphoric acid to-, form reaction products which are retained inthe catalyst In any event, the nitrogen compounds become strongly enough associated with the catalyst that they are resistant toa removal fromnhe catalyst under conditions normally involved in the polymerization. a

According to'the present invention, a novelmanner is provided for treating solid phosphoric acid catalyst to nitrogen compounds from the used solid phosphoric acid catalyst. Since these nitrogen compounds have a detrimental effect on the activity of the catalyst, their remov according to the invention is a beneficial result.

Contacting solid phosphoric acid catalyst with lower" fatty acid generally results in substantially-completere moval of free phosphoric acid, defined as that phosphoric acid which is removable from the catalyst by water at room temperature, as well as of nitrogen compounds. Lower fatty acid contacting at room temperature does not remove any substantial amount of combined phosphoric acid, defined as that which is removable by water at its boiling point but not at room temperature, but does provide good removal of nitrogen compounds, which water is incapable of doing. Typically, a solid phosphoric acid catalystmay contain about 12 weight percent of free phosphoric acid and about 20 weight percent of combined phosphoric acid.

In one embodiment, the contacting with fattyacid according to the invention is performed in the presence of added phosphoric acid in order to inhibit the removal of free phosphoric acid together with nitrogen compounds sequent to the contacting with phosphoric acid.

by the fatty acid. Thus, a solutionof phosphoric acid in either anhydrous or aqueous fatty acid can be employed as the treating agent. Alternatively, the contacting can be performed in the absence of added phosphoric' acid, and the phosphoric acid which is removed thereby-from the catalyst can be replaced by a subsequent treatment of the catalyst with aqueous phosphoric acid or other suitable impregnant. :In either embodimerit, a conventional calcining can be performed sub- The effluent from the catalyst treatment according to. the invention usually contains fatty acid, nitrogencompounds,"phosphoric acid and tarry materialv or polymer which was deposited on the catalyst during-the poly-:

remove-the nitrogen compounds which have contaminated the catalyst as a result of the contact with the polymerizationcharge stock. This accomplished'by contacting the; solid -phosphoric acid catalyst with afatty acid or anhydridecontaining 1 to 3 carbon atoms per molecule. The contactingis, performed in liquid phase at a temperaturefgenerally, withinfthe approximate range from roomftemperature re the boiling point of the acidemployed. Generally,lthe' temperature'will be within the approximate range from C. to 150 C. Elevated temperatures favor more nearly complete removal of basic nitrogen. Elevated pressure can be employed if desired in the contactingwith fatty acid, although it is generally preferable to operate at atmospheric pressure. The fatty acid is preferably employed in the anhydrous state, although itlis, within athe scope of the invention to employ an aqueous-solution ofthe fatty acid or fatty acid containing a small amount of water. V

has 'beenfound that'contacting with fattyacid is capabl'e'ofl about removal of the bulk of basic merization and removed by the fatty acid. The latter is capable of removing a largeproportion, e.g. 60% or more, of the tar and polymer, even at room-temperature; More complete' removal of tar. and polymer can ifdesired be obtained by prior or subsequent treatment with acetone or some other solvent for such materials.

The fattyvacid is preferably distilled from the efiiuent. from the catalyst treatment and re-used to contact ad-. ditional catalyst. The'distilled fatty acid can. if desired; be used to. treat additional solid phosphoric acid containing nitrogenous contaminants. The residual pho s-- v phoric acid can be separated from tar and polymer by selectively'dissolving the acid in water and separating solu tion from undissolved material; it can then if desired be used to impregnate solid adsorbent, which may be-either fresh adsorbent or that previously treated according to theinvention; the impregnated adsorbent is calcined in conventional manner, and used as a polymerization catalyst. Y

In one embodiment, the contacting with fatty'acid is performed in the presence of an aromatic hydrocarbon, preferably having not more than 15 carbon atoms, e.g. benzene, Xylenes, naphthalene, methyl naphthalene, methyl isopropyl benzenes, etc., and this contacting is followed by a contacting with a treating agent consisting essentially of fatty acid. The first contacting removesphosphorus compounds from the original adsorbentyleav ing it in suitable condition for impregnation withad ditional phosphoric acid, which may be eitherfresh" phoric acid or that which was removed in the first contacting. Generally similar results are obtained, employing aliphatic hydrocarbons, preferably those having to 15 carbon atoms, e.g. pentane, petroleum naphtha, polymer gasoline produced in the polymerization of propylene or other olefin, etc., in place/of the atomatic hydrocaibons. Hydrocarbons generally, including cycloaliphatic hydrocarbons, such as cycloh'exane, methyl cycl'ohexane, etc., can be employed in this embodiment.

The contacting with fatty acid according to the invention can be performed in the presence of any suitable added solvent or diluent, such as acetone or other lower aliphatic ketone (up to 6 carbon atoms), methanol or other lower alkanol (up to 6 carbon atoms), carbon tetrachloride, diethyl ether, chlorinated hydrocarbons, fluorinated hydrocarbons, or those referred to previously, etc.

Where mixtures are employed, it is preferred that each component be present in at least 10 volume percent, more preferably 25%, concentration based on total mixture.

The following examples illustrate the invention:

Example I Solid phosphoric acid is employed in the polymerization of propylene at about 400 F. and about 1000 p.s.i.g. for a period of 5-0 days. The solid phosphoric acid catalyst is prepared by contacting granular kieselguhr with aque-' ous phosphoric acid, and calcining the resulting material at a temperature of about 600 F. At the conclusion of the polymerization period, the catalyst contains 1.11% basic nitrogen, as determined by the Kjeldahl technique. The used catalyst containing 1.1 1% basic nitrogen is contacted for minutes with glacial acetic acid at the boiling point of the acetic acid. The amount of acetic acid employed is ml. per gram of catalyst. At the end of the contacting period, the glacial acetic acid is separated from the catalyst and analyzed for basic nitrogen content. The acetic acid contains 1.07% basic nitrogen based on catalyst. Thus, nearly complete removal of basic nitrogen from the catalyst is obtained.

Example [I acid being at room temperature however and for a period of about 16 hours. The original deactivated catalyst contains about 0.36% basic nitrogen and about 12.4% free phosphoric acid. About 80% of this basic nitrogen, at major amount of the tar and polymer on the catalyst, and all of the free phosphoric acid are removed. Acetic acid distilled from the resulting liquid phase and re-used to' contact additional catalyst for removal of nitrogen com pounds. Phosphoric acid in the residue is taken up in water and the solution is separated from tar and polymer and used to contact the previously treated catalyst and deposit phosphoric acid therein. The catalyst is then calcined at about 600 F. and re-used in polymerization of propylene.

Example III Operation generally similar to that in Example 11 is" carried out, using however an equal volume mixture of glacial acetic acid and acetone in place of acetic acid. About 67% of the basic nitrogen, all of the free phosphoric acid, and a greater proportion of tar and polymer than in Example 11 are removed from the catalyst.

Example IV Operation generally similar to that in Example I! is carried out, using however an equal volume mixture of glacial acetic acid and benzene in place of acetic acid. All of the phosphoric acid, but only about 22% of the basic nitrogen compounds, are removed from the catalyst: Ina subsequent treatment of the catalyst with glacial acetic acid in the manner d9 ribed in Example II, the

- a 4 lk. the rm ialaaha nitr en. sqrnr aas aar moved from the catalyst. Acetic acid and benzene are distilled from the first efllue'nt, and acetic acid from the second eflluent. The phosphoric acid in the residue from the first effluent is used to re-impregnate the catalyst after the second treatment. The, residue from the second efilu- 6111 b tant a l re afn isr g i gr ts-a t? carded. G'erferally 'sirnila'rresults are obtained employing polymer gasoline in place of benzene in the first contacting. V 7 Example V Operation generally similar to that in Example 11 is carried out, using however an equal volunremixture, of glacial acetic acid and phosphoric acidin place of the acetic acid. A large proportion of th basic nitrogen compounds is removed, while the phosphoric acid in the treating agent largely inhibits the removal of free phosphoric acid from the catalyst by the treating agent.

Example VI Operation generally similar to that in Example II is carried out, using however acetone in place of acetic acid. All of the phosphoric acid, but only about 19% of-the basic nitrogen compounds, are removed from the'cat alyst. A greater proportion of the tar and polymer than in Example 111 is removed from the catalyst. In a subsequent treatment of the catalyst with glacial acetic acid in the manner described in Example 11, bulk of the remaining basic nitrogen compounds are remtived from the catalyst. Acetone is distilled from the first efilu ent. Subsequent operation is generally similar to that (165 7 scribed in Example IV. Other lower aliphatic ketoifes can be similarly used;

Generally similar results to those described abo'ye" obtained using formic acid or propionic acid iii'place' of,

or in addition to, acetic acid. Generally similar results;

. are alsoobtained employing fatty acid contacting agents containing water.

' The invention claimed is I v r 1. Process for reactivating solid phosphoric acid can alyst which Campinas: contacting solid phosphoric acid catalyst, which has been employed in the enmeriz'afiaii' of gaseous olefins containing nitrogenous impurities, first treatment step at room temperature with a contact ing agent selected frcni the group consisting or (b); ture of a fatty acid containing 1 to 3 carbonates-us "r molecule and a hydrocarbon having 5 to 15 carbon drains; each component of said mixture being present in at leat 10 volume percent concentratitin; (b) a lower phatic ketone' containing up to s'eariien atofntilv ihcrchif substantially, all of the free phosphotic acid iii the: and a minor amount of the basic nitrogen emfi eufias in the catalyst are removed s'ubs eque'ntly treat 4 alyst in a second treatment step at' room temperatt'ir'e with the said fatty acid alone and W from catalyst having reduced content" of nitrogen com-' pounds as a result of said contacting;

References Cited in theme of this patent UNITED STATES PATENTS 2. 19.433 'Hol i a 1. pee; i931 2,658,933 May et 1, Nev. 10, 1353 2,749,359 Calkins et a1. :.;.':..'Iune' s; 1956 

1. PROCESS FOR REACTIVATING SOLID PHOSPHORIC ACID CATALYST WHICH COMPRISES: CONTAINING SOLID PHOSPHORIC ACID CATALYST, WHICH HAS BEEN EMPLOYED IN THE POLYMERIZATION OF GASEOUS OLEFINS CONTAINING NITROGENOUS IMPURITIES, IN A FIRST TREATMENT STEP AT ROOM TEMPERATURE WITH A CONTACTING AGENT SELECTED FROM THE GROUP CONSISTING OG (A) A MIXTURE OF A FATTY ACID CONTAINING 1 TO 3 CARBON ATOMS PER MOLECULE AND A HYDROGEN HAVING 5 TO 15 CARBON ATOMS, EACH COMPONENT OF SAID MIXTURE BEING PRESENT IN AT LEAST 10 VOLUME PERCENT CONCENTRATION, AND (B) A LOWER ALIPHATIC KETONE CONTAINING UP TO 6 CARBON ATOMS, WHEREBY SUBSTANTIALLY ALL OF THE FREE PHOSPHORIC ACID IN THE CATALYST AND MINOR AMOUNT OF THE BASIC NITROGEN COMPOUNDS IN THE CATALYST ARE REMOVED, SUBSEQUENTLY TREATING THE CATALYST IN A SECOND TREATMENT STEP AT ROOM TEMPERATURE WITH THE SAID FATTY ACID ALONE AND SEPARATING FATTY ACID FROM CATALYST HAVING REDUCED CONTENT OF NITROGEN COMPOUNDS AS A RESULT OF SAID CONTACTING. 